Towards environmentally friendly processes in materials and energy technologies probed by beta decayed spin spectroscopy and other physical methods

这项研究的最终目标是启动可持续的自由基和辐射诱导过程，以开发具有潜在技术应用的新材料。这项研究的不同阶段是：*1）基于粒子加速器和计算方法的微观研究; *2）在Mt. Allison，使用我们从1获得的光谱和理论分析的微观理解进行优化; *3）用各种物理方法表征湿实验室合成的产物，如果需要，包括基于粒子加速器的方法（例如，材料的磁性或电子结构特性的研究）。这一循环需要进行多方面的研究，重点如下：*1）绿色溶剂中的自由基和辐射化学; *2）利用工业或自然界的可持续原料或废物，通过自由基和辐射化学开发增值材料;*3）研究有或没有外部场的这种过程的能源效率。* 我们将通过寻找最节能、最环保的溶剂，最大限度地减少自由基方法对环境的影响。我们将实验温度，压力和外部场（如激光或微波（MW））对自由基反应的影响，以找到最有效的方法，并了解这些外部场对自由基反应机理的影响。* 我们计划制造的新材料将是：*1）在溶解CO2的质子离子液体中进行自由基反应的材料 * 我们在离子液体（IL）、超临界CO2、高温化学和活性自由基方面拥有专业知识。因此，我们以前的研究的一个自然的延伸是将CO2溶解在热稳定的离子液体中，然后在该系统上进行自由基反应。我们将专注于修改我们最近合成的热稳定的质子离子液体，但与改性的阴离子（阴离子与氟取代具有良好的可吸收性与CO2），以吸收CO2，使用高温，和自由基前体转化CO2通过自由基反应的商品化学品。* 这些可能在电池，燃料电池，电池或燃料电池或其他应用的离子聚合物的单体组分中具有潜在的应用。2)基于金属或金属氧化物纳米颗粒表面上的自由基反应的新型纳米复合材料。我们希望了解这些系统，因为自由基是许多催化过程和制造聚合物纳米复合材料的中间体。这些研究的好处将包括了解如何：控制或在纳米粒子表面产生新的结构，调整纳米粒子表面的电子和磁性，以及评估纳米粒子对辐射化学的影响。*3）基于与来自生物质或废物的酸的烯醇形式的自由基反应的新材料。我们将对生物质中的烯醇类物质或生物质转化为燃料过程中的中间体进行自由基反应（例如溴化和聚合）。*本论文的主要研究成果如下：1）分子量对自由基反应影响的原位研究，在国内外尚属首次，为分子量对自由基反应影响的原位研究开辟了新的领域。这将有助于解决有关微波非热效应的争议。2)开辟了与酮平衡的烯醇的原位自由基转化领域，以将酸（或具有C=O或C=N基团的任何化合物）从生物质转化为有价值的材料。3)首次探测纳米粒子表面活性自由基的电子结构和反应性。

The ultimate goal of this research is to initiate sustainable free radical and radiation-induced processes to develop novel materials with potential applications in technology. The different stages of this research are: *1) microscopic studies with particle-accelerator-based and computational methods; *2) "wet lab" work at Mt. Allison, optimized using our microscopic understanding gained by spectroscopic and theoretical analysis from 1; *3) characterization of the products of the wet lab syntheses with a variety of physical methods, including particle-accelerator based methods if need be (e.g. studies of magnetic or electronic structure properties of the material).*This cycle calls for multifaceted research that will be performed with following foci: *1) free radical and radiation chemistry in green solvents; *2) using sustainable feedstock or waste products of industries or nature to develop value-added materials by free radical and radiation chemistry; and *3) studying the energy efficiency of such processes with or without external fields. *We will minimize the impact of our free radical methods on the environment by finding the most energy-efficient, environmentally friendly solvents. We will experiment with the effects of temperature, pressure, and external fields (such as lasers or microwave (MW)) on free radical reactions to find the most efficient methodology, and to understand the effects of such external fields on the mechanism of free radical reactions. *The novel materials that we plan to make will be: *1) material from free radical reactions in protic ionic liquids dissolved CO2*We have expertise in ionic liquids (ILs), supercritical CO2, high temperature chemistry and reactive free radicals. Therefore a natural extension of our previous studies is to dissolve CO2 in thermally stable ILs then perform free radical reactions on the system. We will focus on modifying our recently synthesized thermally stable protic ILs, but with modified anions (anions with fluorine substitutions have good miscibility with CO2) to polarize CO2, use high temperatures, and free radical precursors to transform CO2 by free radical reactions to commodity chemicals. *These may have potential applications in batteries, fuel cells, components of monomers for ionic polymers for batteries or fuel cells or other applications.*2) Novel nanocomposites based on free radical reactions on the surface of metal or metal oxide nanoparticles. We hope to understand these systems, since free radicals are intermediates in many catalytic processes and for making polymer nanocomposites. *The benefits of these studies will include understanding how to: control or generate new structures on the surface of nanoparticles, tune the electronic and magnetic properties on the surface of nanoparticles, and evaluate the effects of nanoparticles on radiation chemistry. *3) Novel materials based on free radical reactions with enol forms of acids from either biomass or waste products. We will do free radical reactions (e.g. bromination and polymerization) on enol type forms of material in biomass or intermediates in the process of biomass conversion to fuel.*The impacts of our studies are the following: 1) The in situ studies of the effects of MW on free radical reactions have never been done before and we will open the field by our studies. This will help to solve the controversies regarding non thermal effects of MW. 2) Opening the field of in situ free radical transformation of enols in equilibrium with ketones to transform acids (or any compound with C=O or C=N group) from biomass to valuable material. 3) For the first time probing the electronic structures and reactivity of reactive free radicals on the surface of nanoparticles.